The design and synthesis of electroactive and magnetic polymers

Citation

Rock, Michael M., Jr. (1993) The design and synthesis of electroactive and magnetic polymers. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/w5nj-m257. https://resolver.caltech.edu/CaltechTHESIS:01082013-155858039

Abstract

Ring-opening metathesis polymerization (ROMP) remains a valuable tool in polymer synthesis because it affords structurally well-defined, functionalized materials with highly unsaturated polymer backbones. The power and flexibility of organic and polymer chemistry are used here to create fully conjugated, electroactive organic polymers.

A series of electroactive poly(norbornadienebenzoquinone-imine) and poly(norbornadienebenzoquinone) polymers have been synthesized by the ring-opening metathesis polymerization (ROMP) of functionalized bicyclo[2.2.1]hepta-2,5-dienes using alkylidene metathesis catalysts. Incorporation of these quinone and imine redox units into organic norbornadiene polymers generates highly reactive and conductive materials capable of charge storage and electrochromism.

In a second effort, we describe an improved precursor polymer route to polyparaphenylene (PPP) based upon the ring-opening metathesis polymerization (ROMP) chemistry of cis-di(3,4- dihydroxymethyl)cyclobutene dicarbonate. These precursor polybutenamers undergo a final conversion, under mild reaction conditions, to insoluble polyparaphenylene (PPP) without destroying or disturbing the existing polymer structure. These polybutenamers, in addition to their success in PPP conversion, are of great interest because they incorporate high degrees of acid, oxygen, and hetereoatom functionality into a soluble 1,4-poly(butadiene) structure.

Finally, organic magnets offer new insights into the nature of magnetism and lead to the development of materials with unique optical, electrical, and magnetic properties. To test the claims and postulates of the Topological Coupling Model, an organic-based ferromagnetic polymer was designed around the ring-opening metathesis polymerization (ROMP) of 3-diphenylmethylenecyclobutene. Doping, the generation of charged species along the polymer, generates a radical spin (1/2) on every monomer unit in the polymer chain, resulting in a fully conjugated polybutenamer polymer with active spin centers every five (5) carbons apart. Oxidative doping of this material evokes ferromagnetic couplings among unpaired spins in the material.

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